US3326977A - Process for preparing polymeric sulfides - Google Patents

Description

United States Patent 3,326,977 PROCESS FOR PREPARING POLYMERIC SULFIDES Dee L. Johnson and Delbert D. Reynolds, Rochester,

N. Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Jan. 12, 1962, Ser. No. 165,931 9 Claims. (Cl. 260-584) This application is a continuation-in-part of the copending Johnson and Reynolds US. patent application Serial No. 80,970, filed January 6, 1961, now abandoned.

This invention concerns a process for preparing polymeric sulfides and, more particularly, polymers in which the repeating unit is a derivative of ethylene sulfide. These polymers will hereinafter be referred to as oligoethylene sulfides.

In Reynolds US. patent application Serial No. 721,678, filed March 17, 1958, it is shown that introduction of a mercaptoethyl group into a substance such as an amine or mercaptan yields a nonpolymeric mercaptoethyl derivative. The reaction described therein was' carried out in a solvent medium such as toluene or dioxane, which medium is nonpolar or very slightly polar.

It is the object of our invention to produce polymeric sulfides. A further object is to introduce into organic substances more than one mercaptoethyl group such that oligoethylene sulfides are obtained.

These objects are accomplished byv a process for preparing polymeric sulfides of the general formula where r may be 1 or 2, R'- may be hydrogen, hydroxymethyl, or alkyl (C -C n is an integer from 2 to 20,

and X is (a) i i G C O)m m being 0 to l, where r is l, G may be RHN-, RRN, and ZN, where R is alkyl (C -C cycloalkyl, aralkyl, or aryl and Z may be 4 or 5 carbon or oxygen atoms necessary to complete a heterocyclic ring with N, and when r is 2, G may be' or RRNN=, where Y is hydrogen or R (defined above) and x is 2 to 18; (b) H N; (0) HO; (d) RS (R defined above); and (e) RO- (R defined above); comprising reacting QCO-ACH -CHR'BH, where Q is an alkoxy group of 1 to 18 carbon atoms, or, together With the hydrogen atom of B (i.e. to form QH), is a covalent bond forming a heterocyclic ring; R is defined as above; and A and B are dissimilar and may be selected from the class consisting of sulfur and oxygen; with a nucleophilic initiating agent chosen from the group consisting of (l) XH, Where X is G (defined above), Na0, KO, and NH O, and (2) XM, where X is RO and RS (R defined above) and M is an alkali metal, in a mercaptide ion-enhancing medium.

The bringing together of the reactants of our process in a medium which enhances or promotes the formation of mercaptide ions is critical for the performance of our invention to produce oligoethylene sulfides. If the reactants are placed in a medium which inhibits the formation of mercaptide ions, such as the media found in Reynolds, application Serial No. 721,678 (now abandoned), mentioned above, then the desired polymerization process does not occur.

The mercaptide ion-enhancing medium is most easily obtained by placing the process reactants in a solvent which induces ionization. Such solvents include alcohols, water, acetonitrile, propionitrile, dialkylformamides, and

3,326,977 Patented June 20, 1967 the like. In general solvents considered polar solvents are operable. It will be readily apparent that in many instances the desired mediumis obtained from one of the process reactants. For example, when the process reactant is itself an alcohol, a mercaptan, or a strongly basic amine, such as aliphatic amines or hydrazines, then additional solvent is optional and may even be a nonpolar or weakly-polar one. For certain process reactants such as weakly-basic amines, e.g. aromatic amines, the mercaptide ion formation is induced by the addition to the reaction mass of an alkali metal alkoxide, for example sodium methoxide. In any of above-mentioned routes, the necessary mercaptide ion-promotion medium is established for the reactants and the desired polymerization process is operable therein.

One of the reactants necessary for operating our process is Q-COA-CH -CHR'--BH in which Q is an alkoxy group of l to 18 carbon atoms, or, together with the hydrogen atom of B (i.e. to form QH), is a covalent bond forming a heterocyclic ring; R is hydrogen, hydroxymethyl or alkyl (C -C and A and B are dissimilar and may be selected from the class consisting of sulfur and oxygen. Representative compounds which we find useful include ethylene monothiolcarbonate,

II 0 substituted ethylene monothiolcarbonates, alkyl 2-hy- 'droxyalkylthiolcarbonates, and alkyl 2-mercaptoethyl-carphase solvent system is used employing water and an immiscible inactive solvent, such as benzene, petroleum ether, or the like. The alkyl 2-mercaptoethylcarbonates are prepared by isomerizing the corresponding alkyl 2- hydroxyethylthiolcarbonates. For example, n-hexyl 2- mercaptoethylcarbonate may be prepared in a 200-ml. flask equipped with a 14-inch packed column, and a variable-rate still-head. In the flask is placed 103 grams (0.5 mole) of n-hexyl 2-hydroxyethylthiolcarbonate and 0.002 gram of uranyl acetate. The system is placed under vacuum and distilled, producing 85 grams or 82 percent yield of n-hexyl Z-mercaptoethylcarbonate (boiling point /0.2 mm., refractive index 1.4542, 99.5 percent pure by iodometric titration). Similarly treating 2-mercapto-l,3- propanediol or'2- mercapto-l-alkanols with an alkyl chloroformate yields alkyl lhydroxymethyl 2 hydroxyethylthiolcarbonate or alkyl l-alkyl 2 hydroxyethylthiolcarbonate, which on isomerization yield, respectively, alkyl 2-hydroxymethyl 2 mercaptoethylcarbonate and alkyl 2-alkyl-2-mercaptoethylcarbonates. Ethylene monothiolcarbonate may be prepared from phosgene and 2- mercaptoethanol as described in US. Patent No. 2,828,- 318 (Reynolds) which issued March 25, 1958. Similarly hydroxyrnethyl and alkyl substituted ethylene monothiolcarbonates may be obtained by replacing Z-mercaptoethanol with the appropriately substituted 2-n1ercaptoethanolic compound. The preferred members of the Q-COACH CHR'-BH family are ethyl 2-mercaptoethylcarbonate, ethylene monothiolcarbonate, and ethyl 2-hydroxyethylthiolcarbonate.

The other reactant of our process is a nucleophilic initiating agent chosen from the group consisting of (l) XH, where X is G- (defined above), NaO-, KO-, and NH O, and (2) XM, Where X is RO and RS (R definedabove) and M is an alkali metal. Representative examples of nucleophilic initiating agents which are perable in our process include primary and secondary aliphatic, alicyclic, aromatic, aralkyl and heterocyclic amines; primary and secondary aliphatic and heterocyclic diamines; aliphatic and aromatic hydrazines; sodium hydroxide; potassium hydroxide; ammonium hydroxide; the sodium, potassium, or lithium salts of alkanols, cycloalkanols, aralkanols, phenols and the like; and the sodium, potassium, or lithium salts of mercaptans such as alkauethiols, cycloalkanethiols, aralkanethiols, thiophenols, and the like. When the nucleophilic initiating agent contains more than one functional group as in alkanolamines,

mercaptoalkanols, and the like, the hydroxyl group being the least strong initiator is to be considered for the purposes of our invention only a substituent of the amine, mercaptan, and the like. In certain instances it will be convenient to prepare the nucleophilic initiating agent in situ by adding convenient precursors to the reaction vessel. For example, ammonia and water may be used for in sit-u ammonium hydroxide. Similarly free alcohol or mercaptan and alkali metal or alkali metal alkoxide may be added as a pair to obtain'the ROM or RSM in situ. Our preferred nucleopholic initiating agents include ethonolamine, N-methylethanolamine, diethanolamine, 2-amino- 2-methyl-l-propano-l, 2-a-mino-2-rnethyl-l,3 propanediol, 2-amino 2 (hydroxymethyl) 1,3 propanediol, ndecylamine, cyclohexylamine, morpholine, ethylamine, diethylamine, benzylamine, aniline, a,a,a-trifluorotoluidine, ethylenediamine, piperazine, N,N-dimethylhydrazine, sodium hydroxide, ethanol (as the alkoxide), benzyl alcohol (as the alkoxide), l-butanethiol (as the alkali metal mercaptide), p-thiocresol (as the alkali metal mercaptide), and 3mercapto'-1,2 propanediol (as the alkali metal mercaptide).

In general the process for preparing oligoethylene sulfides is conveniently simple. The reactants with or without additional solvent, as needed to produce the mercaptide ion-promoting medium, are mixed in a vessel at room temperature and the nucleophilic initiating agent induces practically instantaneous reaction. To achieve highest yields of polymer, one may optionally heat at reflux temperature of any liquid present in the reaction vessel for a short period, say one to two hours. Any remaining extraneous liquids, such as original solvent or unchanged starting reactant, may be removed by distillation at reduced pressures, the desired polymer remaining. In many instances, the molecular weight of the polymer is such that the desired polymeric product precipitates from the reaction medium and may be separated by simple filtration.

In certain instances the structure of the desired polymeric product can influence the choice of reaction conditions. When the nucleophilic agent is an unhindered amine, for example n-butylamine, an intermediate 2- mercaptoethyl N-n-butylcarbamate forms rapidly and in temporary excess, in the reaction with ethylene monothiolcarbonate. This intermediate is strongly nucleophilic and, being present in an excess, leads to the oligoethylene sulfide (i.e.v in general. formula 111:1). When the amine is hindered, for example tert.- butylamine, the intermediate, Z-mercaptoethyl N-tert.- butylcarbamate, is not formed rapidly and in excess, and

the original hindered amine remains the nucleophilic agent producing the oligoethylene sulfide tert.

C H NH (CI-I CH H (i.e. in general formula m=0). To obtain aminooligoethylene sulfide (i.e. m=0) from an unhindered amine like n-butylamine, the amine nucleophilic initiating agent must be kept in excess by the simple expediency of placing it in the reaction vessel first and slowly adding ethyl 2-mercaptoethylcarbonate to obtain n-C H NH(SH CH S) ,H (i.e.

The oligoethylene sulfides prepared by the process of our invention are useful silver complexing agents and can be used in various photographic systems. In electrophotography, these polymers are especially Valuable as constituents in electrolytic developing solutions. for singlestep direct image-forming photoconductographic processing as described in D. L. Johnson et al., US. Serial No. 117,125, filed June 14, 1961, now US. Patent No. 3,072,542. In silver halide photographic systems they are useful as fixers or stabilizers. In silver halide diffusion transfer processing they improve the tone of silver images.

The following examples are intended to illustrate our invention but not to limit it in any way.

Example 1.1,1 dimethyl 2 hydraxyethylaminooligo ethylenesulfide One mole (89 g.) of 2-amino-2-methyl-l-propanol was dissolved in 1 liter of dioxane brought to reflux under an effective condenser as 1 mole (150 g.) of ethyl-2- mercaptoethylcarbonate was added dropwise in 1.5 hours. The mixture was refluxed 0.5 hour, then stripped of solvent and some excess amine. The product (99 g.) was the residue in the flask with an average molecular weight (by I titration) of 263 or 2.9 repeating ethylene sulfide units.

Example 2.1,1(dihydr0xymethyl) ethylaminooligoethylenesulfide To a solution of 1 mole g.) 2-amino-2-methyl- 1,3-propanediol in 1 liter of diOXane at reflux under an eifective condenser was added 1 mole g.) ethyl-2- mercaptoethylcarbonate dropwise in 1.5 hour- The mixture was refluxed an additional 0.5 hour then stripped of solvent under aspirator vacuum. The product was the residue in the flask with a molecular weight of 311 or 3.43 repeating ethylene sulfide units.

Example 3 .Tris-(hydr0xymethyl methylaminooligoethylenesulfide To a refluxing solution of 121 :g. (1 mole) 2-amino-2- hydroxymethyl-1,3-propanediol' and 500 ml. dioxane-SOO rnl. tetrahydrofurfuryl alcohol was added 150 g. (1 mole) ethyl Z-mercaptoethylcarbonate dropwise in 1 hour. The reaction mixture was refluxed 1 hour additional and stripped of solvent. The product was the residue in the flask, 174 g. with a molecular weight 293. or 4.88 repeating ethylene sulfideunits.

Example 4.2-hydr0xyethylamino-oligoethylene sulfide Three moles g.) 2-arninoethanol were dissolved in 1.4 liter of toluene and 800 ml. of dioxane and brought to reflux under an efficient condenser. To this solution was added 1 mole (150 g.) of ethyl Z-mercaptoethylcarbonate dropwise in 2.5 hours. After addition the mixture was refluxed 2 hours. The solvent and excess amine were stripped by vacuum distillation leaving 104 g. of a viscous oil N 1.5338. By iodometric titration the product had an average molecular weight of 142 which indicates an average of 1.35 repeating ethylene sulfide units. The calc. value for C2H7NO(C2H4S)1 35 is C, 39.4; H, 8.7; N, 9.9; S, 30.4. Found: C, 39.6; H, 8.8; N, 9.9; S, 29.9.

Example 5 .n-Butylamino-oligoe-thylene sulfide To a refluxing solution of g. (0.2 mole) n-butylamine 30 ml. water and 200 ml. methanol was added dropwise in 30 minutes. 30 g. (0.2 mole) ethyl Z-mercaptoethylcarbonate. Refluxed 1 hour duringwhich time the alcohol was boiled 01f. Cold water was added and the white powder was collected having a molecular weight of 690 or 10.4 repeating ethylene sulfide units.

Example 6.-n-Decylamino-oligoethyIene sulfide Sixteen grams (0.1 mole) n-decylamine, 100 ml. methanol and 100 ml. water were refluxed on a steam bath while 30 g. (0.2 mole) ethyl Z-mercaptoethylcarbonate was added dropwise in 30 minutes. After refluxing an additional hour the white solid was collected after adding ice and washed with ethanol yielding 13 g. of product with a molecular weight of 1214 or 17.2 repeating ethylene sulfide units.

Example 7 .Amino-oligoethylene sulfide Ethyl Z-mercaptoethyl carbonate, 60 g. (0.4 mole) was added dropwise in 30 minutes to 250 ml. concentrated ammonium hydroxide at 40. After the addition was complete 250 ml. concentrated ammonium hydroxide was add: ed and the thick mixture was heated 15 min. on a steam bath. The white product was collected by vacuum filtration, washed with cold water to yield a powder with a molecular weight of 471 or 7.6 repeating ethylene sulfide units.

Example 8.Bis(2-hydr0xyethyl) amino-oligoethylene sulfide To a vigorously refluxing mixture of 105 g. (1 mole) 2,2-iminodiethanol and 0.5 liter dioxane under an effective condenser was added 150 g. (1.0 mole) ethyl Z-mercaptoethylcarbonate dropwise in 1 hour. The reaction was refluxed 1 hour, stripped of solvent leaving 120 g. of product having a molecular weight of 347 or 5.79 repeating ethylene sulfide units.

Dimethylamino-oligoethylene sulfide Twenty two grams (0.5 mole) dimethyl amine were dissolved in 500 ml. water, warmed on a steam bath to which was added 150 g. (1.0 mole) ethyl 2-mercaptoethyl carbonate dropwise in 1 hour with an additional 2 hour reflux. The white powdery 'product had a molecular weight of 495 or 7.5 repeating ethylene sulfide units.

Di-n-dodecylamino-oligoethylene sulfide To a refluxing solution of 35.3 g. (0.1 mole) di-ndodecylamine and 500 ml. methanol was added 75 g. (0.5 mole) ethyl 2-mercaptoethylcarbonate dropwise in 30 minutes. After refluxing overnight a soft solid product was obtained with a molecular weight of 679 or 5.43 repeating ethylene sulfide units,

Example 9.--Benzylamino-oligoethylene sulfide Example 10.N-methylberzzylamino-oligoethylene sulfide To a refluxing solution of 30 g. (.25 mole) N-methylbenzylamine, 250 ml. water, and 250 m1. methanol was added 150 g. (1.0 mole) ethyl Z-mercaptoethylcarbonate dropwise in 1 hour. The mixture was refluxed 2 hours more and the white soli-d collected had a molecular weight of 456 or 5.58 repeating ethylene sulfide units.

Example 11 -Ethyl mereapto-oligoethylene sulfide Example 12.-Mercapto-0lig0ethylene sulfide Hydrogen sulfide was passed into 500 ml. of heated (steam bath) concentrated ammonium hydroxide solution for 30 min. To this was added 150 g. (1 mole) ethyl Z-mercaptoethylcarbonate dropwise in 30 min. The

' mixture was then refluxed overnight and a white polymeric powder collected with a molecular weight of 531 or 8.3 repeating ethylene sulfide units.

Example 13.-Benzylmercapto-oligoethylene sulfide To a solution of 30 g. (0.25 mole) of benzenemethanethiol 11 g. (0.25 mole) sodium methoxide and 300 ml. N-methylpyrrolidone heated on a steam bath was added 225 g. (1.5 mole) ethyl Z-mercaptoethylcarbbnate dropwise in 3 hours. A clear solution resulted which upon cooling precipitated 98 g. of white solid which was triturated with ether. The solid has a molecular weight of 1200 or 18 repeating ethylene sulfide units.

' Example 14.N-ethylanilino-oligoethylene sulfide Example 15 .2- (ethoxyethoxy -eth0xy-0lig0ethylene sulfide Six grams (0.3 mole) sodium was added to 500 ml. 2-(ethoxyethoxy)-ethanol and heated on a steam bath. To this solution was added 150 g. (1.0 mole) ethyl 2-mercaptoethylcarbonate dropwise in 1 hour. Subsequently the reaction was refluxed 1 hour. The white precipitate was collected by vacuum filtration triturated with ether yielding 60 g. with a molecular weight of 1109 or 16.3 repeating ethylene sulfide units.

Example 16.Eth0xy0lig0ethylene sulfide Six grams (0.3 mole) sodium was dissolved in 175 ml. ethanol brought to reflux and 36 g. (0.24 mole) ethyl 2- mercaptoethylcarbonate added dropwise in 30 min. After an additional 30 min. reflux the white polymeric powder was collected, triturated in ether and had a molecular weight of 440 or 5.57 repeating ethylene sulfide units.

7 Example 17.Benzyloxyoligoethylenesulfide 'A solution of 6 g. (0.3 mole) sodium and 500 ml. benzyl alcohol was heated on a steam bath while g. (1.0 mole) ethyl 2-mercaptoethylcarbonate was added dropwise in 1 hour. The mixture was refluxed overnight and upon cooling a soft solid with a molecular weight of 763 or 10.9 repeating ethylene sulfide units was collected. v

Example 18.-Hydr0xy-0ligoethylene sulfide The dropwise addition of 37.5 g. (0.25 mole) ethyl 2- mercaptoethylcarbonate in 30 min. to a solution of 10 g. (0.25 mole) sodium hydroxide :and 300 ml. water heated on a steam bath quickly formed a white solid. After an additional 30 min. reflux the solid was collected and found to have a molecular weight of 346 or 5.5 repeating ethylene sulfide units.

Example 19.Phen'xy-0ligoethylene sulfide To a solution of 219 g. phenol and 16 g. (0.25 mole) sodium methoxide heated on a steam bath was added dropwise in minutes, 75 g. (0.5 mole) ethyl Z-mercaptoethylcarbonate. The white mass liquified and was refluxed 1 hr. and while hot filtered, triturated with 100 ml. ether, then 100 ml. acetone to give 23 g. of white powder with a molecular weight of 1192 or 18.3 repeating ethylene sulfide units.

Example 20.N-butylamino-oligoethylene sulfide Fifteen grams (0.2 mole) n-butylamine, 250 ml. methanol, and 250 ml. water were refluxed on a steam bath. To this solution was added 30 g. (0.2 mole) ethyl 2-hydroxyethylthiolcarbonate dropwise in 20 min. The refluxing was continued 45 min. as the white solid precipitated from solution, was subsequently collected, triturated in water and when dry 12.5 g. had a molecular weight of 740 or 11.1 repeating ethylene sulfide units.

Example 21 .Benzylmercapto aligoethylene sulfide Ethyl 2-hydroxyethylthiolcarbonate (150 g., 1.0 mole) was added dropwise in 30 min. to :a refluxing solution of 30 g. (0.2 mole) benzenemethanethiol and 11 g. (0.2

, mole) sodium methoxide in 250 ml. each of methanol and Example 23.-n-Butylcarbamolylaxy-oligoethy[ene sulfide One-half mole of ethylene monothiolcarbonate and 1.5 mole ofn-butylamine was refluxed in a mixture of 500 ml. of methanol and 500 ml. of water. After 6 hours the solid was separated and dried. Iodometric titration gave an apparent molecular weight of 42.2. A strong carbonyl was shown at 5.96 microns. These data along with elemental analysis indicated its structure as Example 24.-ls0pr0pylcarbamoylaxy-aligoezhylene sulfide and isopropylamina-oligaethylene sulfide One-half mole of ethylene monothiolcarbonate and 1.5 mole of isopropylamine were refluxed together for six hours in a mixture of 500 ml. of methanol and 500 ml. of water. The dried oligomer had an apparent molecular weight of 540. Infrared and elemental analysis indicated that it was a mixture of the oligomers,

(CH CHNHCO CH CH S) H and (CH CHNH (CH CH S H Example 25 .tert.Butylamino-o ligoethylene sulfide One-half mole of ethylene monothiolcarbonate and 1.5 moles'of tert.butylamine were refluxed together in a mixture of 500 ml. of methanol and 500 ml. of water. The dried, white oligomer showed an apparent molecular weight of 503. Its infrared showed no carbonyl band. These data along with elemental analysis indicated the structure tert. 7H.

Analysis.Calcd. for above structure: C, 43.8; H, 7.9; N, 2.8; S, 45.4. Found: C, 43.4; H, 7.9; N, 2.5; S, 45.1.

Example 26.Carbamoyloxy-aligoethylene sulfide One-half mole of ethylene monothiolcarbonate was stir-red into a mixture of 200 ml. of 28% NH OH and 200 ml. of water. A white oligomer separated within a few minutes. The washed and dried product gave a molecular Weight of 297.

In a second experiment the ethylene monothiolcarbonate was added dropwise over a 45 minute period. The apparent molecular weight was 156. The infrared curves were identical for both products and indicated the structure to 'be H NCO (CH CH S) I-I.

Example 27.-n-0ctylcarbam0yloxy oligoethylene sulfide One-tenth mole of ethylene monothiolcarbonate and 0.1 mole of n-octylamine refluxed together for 5 hours in a mixture of 75 ml. of methanol and 75 ml. of water. The polymer was washed and dried. The infrared exhibited a very strong carbonyl indicating the structure to be n-C H NHCO (CH CH S) ,H.

Example 28.--Benzylcarbam0yl0xy-olig0ethylene sulfide Example 27 Was repeated in which the n-octylamine was replaced by benzylamine. Infrared analysis indicated the structure to be C H CH NHCO (CH CH S),,H. It had a molecular weight of 381. An-oligomer of the same structure was obtained when the ethylene monothiolcarbonate was added dropwise over a 60 minute period.

Example 29.N-methylbenzylamino aligoethylene sulfide Example 28 was repeated using N-methylbenzylamine instead of benzylamine. The oligomer was an oil with the structure One-half mole of ethylene monothiolcarbonate and one-half mole of diethylamine were stirred together for 1 hour in a mixture of 200 ml. of water plus 200 ml. 9f methanol. The white oligomer was washed and dried. It contained no carbonyl and its structure is z s 2 z z 11 A second experiment identical in all respects except that the ethylenemonothiolcarbonate was added dropwise had an identical infrared spectrum.

Example 31.-Di-n-burylamina-o ligaethylene sulfide One-tenth mole of di-n-butylamine and 0.1 mole ethylene monothiolcar-bonate were refluxed together for 5 hours in ml. of a 1:1 mixture of methanol and water. The white oligomer contained no carbonyl. The structure was shown to be (n-C H N(CH CH S) H.

Example 32.-Di-sec.buty lamina-aligoethylene sulfide This was identical to Example 31 excepting that disec.butylamino was used instead of di-nbutylamine. There was no carbonyl band in the infrared. The structure was Example 33.M0rp0h0'lin0carbonyloxy-oligoethylene sulfide One-half mole of ethylene monothiolcarbonate plus 1.5 mole of morpholine was refluxed for six hours in a mixture of 500 ml. of water plus 500 m1. of methanol. The-re was little solid present at this stage. The reaction mix ture was distilled through a 14" Vigreux column. After removal of solvents and excess morpholine, 33 g. product was obtained. It was shown by infrared and elemental analysis to be The molecular weight was 286.

Example 35.-n-Decylcarbamoyloxy-oligoethylene sulfide One-tenth mole of n-decylamine and 0.1 mole of ethylene monothiolcarbonate were reacted in 200 ml. of a 1:1 mixture of methanol and water. The ethylene monothiolcarbonate was added dropwise over a 20 minute period. The molecular weight was 1135 by iodometric titration in dimethylformamide. The structure is Example 36.Prpylcarbamoyloxy-olgioethylene sulfide One-tenth mole of ethylene monothiolcarbonate and 0.1 mole of propylamine were refluxed together for five hours in a mixture of 75 ml. of methanol and 75 ml. of water. The white oligomer was washed with water and dried. A strong carbonyl band was exhibited at about 5.95 microns. The structure was shownto be One-half mole of ethylene monothiolcarbonate was stirred into a mixture of 200 ml. of aqueous NaOH plus 200 ml. of dioxane. After 2 hours the oligomer was separated and washed. The product contained no carbonyl group. Its structure was HO(CH CH S) ,H.

From a similar run in which the ethylene monothiolcarbonate was added dropwise over a one-hour period an oligomer of similar structure was obtained. An iodometric titration indicated a molecular weight of 369.

Example 38.-Ethoxy-oligoethylene sulfide 0.5 moles of ethylene monothiolcarbonate was added dropwise over a period of 1 hour to 6 g. of sodium dissolved in 800 m1. of ethanol. An oligomer having the structure C H O(CH CH S), H separated immediately.

Example 39.2-(eth0xyeth0xy)ethoucyoligoethylene sulfide Six grams of sodium was dissolved in 500 ml. of 2- (ethoxyethoxy)ethanol. This solution was heated on a steam bath and 0.5 moles of ethylene monothiolcarbonate was added dropwise. The oligomer which formed had no carbonyl in its infrared spectrum and has the following structure I C2H5OC2H4OC2H4O(CH2CH2S H- Example 40.-n-Decylmereapto-oligo'ethylene sulfide Six grams of sodium was dissolved in a mixture of 300 -ml. of ethanol and 0.25 moles of l-n-decanethiol. This solution was refluxed and 0.5 moles of ethylene monothiolcarbonate was added over a period of 1 hour. The oligomer showed no carbonyl band in the infrared spectrum. It has the structure n-C l-I -S(CH CH S) H.

Example 4] .Benzylmercaptoligoefhylene sulfide This preparation was similar to that described in Example 40 except benzenemethanethiol was used instead of l-n-decanethiol. The oligomer contained no carbonyl and has the structure C H CH S(CH CH S) H.

Exalmple 42..Phenylmercapto-oligoethylene sulfide This preparation was similar to that disclosed in Example 40 except that thiophenol was used instead of 1- n-decanethiol. The oligomer had the structure 10 Example 43.--Phen.oxy-0ligoezhylene sulfide Ten grams of phenol containing 0.25 gm. of sodium was warmed until the sodium dissolved. One hundred ml. of dioxane and 10.4 g. of ethylene monothiolcarbonate was added. The solution was refluxed for 5 hrs. The oligomer was a low molecular weight oil.

Example 44.Did0decylamino-oligoethylene sulfide One-tenth mole of didodecylamine was refluxed for 5 hrs. in ml. of methanol containing 0.2 moles of ethylene monothiolcarbonate. A low molecular weight oil of the structure C H N*(CH CH S),,=H was obtained.

Example 45 .-M ercapto-oligoethylene sulfide Example 46.1,I-dim'ethylhydrazinobis-oligoethylene sulfide To a refluxing solution of 1,1-dimethylhydrazine (180.3 g., 3.0 mole) was added 104g. (1.0 mole) ethylene monothiolcarbonate dropwise in 1 hour. A vigorous reaction ensued precipitating 50 g. of white powder which had a molecular weight 6 68 for a secondary amine with one oligoethylene sulfide chain. Elemental analysis and infrared spectroscopy (absence of the 2.9 micron band for secondary amine) indicates that the product is the his- (oligoethylene sulfide) with the average chain length of 10 units.

Calc. for C H N S C, 40.4; H, 7.5; N, 2.1; S, 49.8. Found: C, 40.4; H, 7.1; N, 1.8; S, 50.1.

Example 47 .Beuzyl0xy-oligoethylene sulfide ml. diethylether g. white powdery solid precipitated with a molecular weight of 606 or the benzylether with 8.3 repeating ethylene sulfide units.

Example 4 8.tert.0cladecy lamina-oligoethylene sulfide Ten grams of tert.octadecylamine and 500 ml. methanol were vigorously refluxed on a steam bath while 104 g. 1.0 mole) ethylene monothiolcarbonate was added in one portion. The clear solution was refluxed 24 hours and upon concentration a white powder separated having a molecular weight of 901 or 9.6 repeative ethylene sulfide units.

The invention has been described in considerable detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

We claim:

1. A process for preparing a compound having the formula wherein r is an integer of from 1 through 2, R is selected from the group consisting of hydrogen, hydroxymethyl, and alkyl of from 1 through 8 carbon atoms, n is an integer of from 2 through 20, and X is wherein, when r is 2, G is selected from the group consisting of and and RRNN=, wherein Y is selected from the group consisting of hydrogen and R, and x is an integer of from 2 through 18, (b) H N- HO- (d) RS, and (e) RO, wherein in (a), (d), and (e), R is selected from the group consisting of alkyl of from 1 through 18 carbon atoms, cyclohexyl, cyclopentyl, benzyl, and phenyl, which process comprises reacting, in a mercaptide ionenhancing medium, (I) a sulfide selected from the group consisting of Q-CO--ACH CHR'BH and UHF-CHE i t II 0 wherein Q is alkoxy of from 1 through 18 carbon atoms, A and B are dissimilar and are selected from the group consisting of sulfur and oxygen, and R is selected from the group consisting of hydrogen, hydroxymethyl, and alkyl of from 1 through 8 carbon atoms and (II) a nucleophilic initiating agent selected from the group consisting of I (i) XH wherein X is selected from the group consisting of. RHN, RRN,

r r HN (CH2) ,N-H

wherein Y is selected from the group consisting of hydrogen and R as above defined, (iii) wherein Y is selected from the group consisting of hydrogen and R as above defined,

(iv) RRN-NH wherein R is as above defined, and

(v) XM wherein X is selected from the group consisting of RO, and RS- wherein R is as above defined and M is an alkali metal.

2. A process according to claim 1 in which the mercaptide ion-enhancing medium is a solvent which induces ionization.

3. A process according to claim 1 in which the starting material is ethyl Z-mercaptoethylcarbonate.

4. A process according to claim 1 in which the starting material is ethylene monothiolcarbonate.

5. A process according to claim 1 in which the starting material is ethyl 2-hydroxyethylthiolcarbonate.

6. Process for preparing 1,1(dihydroxymethyl)ethylamino-oligoethylene sulfide which comprises reacting Z-amino-Z-methyl-1,3-propanediol and ethyl-Z-mercaptoe-thylcarbonate.

7. Process of preparing tris(hydroxymethyl)methylaminooligoethylene sulfide which comprises reacting 2-amino 2 hydroxymethyl 1,3 propanediol and ethyl 2-mercaptoethylcarbonate.

8. Process of preparing 2-hydroxyethylaminooligoethylene sulfide which comprises reacting 2-aminoethanol and ethyl Z-mercaptoethylcarbonate.

9. Process of preparing 1,1-dimethylhydrazinobisoligoethylene sulfide which comprises reacting 1,1-dimethylhydrazine and ethylene monothiolcarbonate.

References Cited UNITED STATES PATENTS 9/1948 Carlson 260-327 1/1963 Johnson et al. 260-327 CHARLES B. PARKER, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 ,326 ,977 June 20 1967 Dee L. Johnson et al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below. Y

Y Column 1, lines 44 and 45, after "-N(CH N-" insert column 3, lines 26 and 27, for "ethonolamine" read ethanolamine column 4, line 14, for "(SH CH S)" read (CH CH S) column 8 line 54 for "sec butylamino" read H sec. butylamine lines 72 to 74, the formula should appear as shown below instead of as in the patent:

column 9 line 62 for "nC H S(CH CH S) l-l" read r 1 C H S[CH CH H column 10, line 22, for

"separated." read separated, column 11, line 46, for "RRN" read RRN- Signed and sealed this 22nd day of October 1968.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. EDWARD J. BRENNER Attesting Officer Commissioner of Patents

Claims (1)

1. A PROCESS FOR PREPARING A COMPOUND HAVING THE FORMULA